Production of plastic masses



Patented 0a. 25, 1932 a, UNITED STATES PATENT OFFICE MARTIN LUTHER,

TO I. G. FABBENINDUSTBIE OPPAU, GERMANY, ASSIGNOBS OF FBANKFOBT-ON-THE-MAIN,

PRODUCTION or rLAs'rIc MASSEB NoDrawing. Original application filed June 3,

Divided and this application nlcd July 19,

The present invention relates to the production of plastic masses.

It is already known that by the destructive oxidation of paraflin hydrocarbons, 'waxes and the like, for example by passing a strong current of air through the initial material in the liquid state preferably while heating and in the presence of fillers possessinga large superficial area, a mixture of organic products containing oxygen is obtained, WhlCll consists mainly of neutral oxygen compounds, saturated fatty acidsand dark colored ac1d products, insoluble in petroleum ether. The acids which are insoluble in petroleum ether may be separated from the saturated fatty acids for example b pressing or sweating or a combination of both these processes.

We have now found that valuable plastic products are obtained by heating that hquid part of the acids obtained by the oxidation of paraflin hydrocarbons, which is insoluble in petroleum ether with organic compounds which contain two or more hydroxyl groups in the molecule to atemperature above about 150 0., if desired with the addition of other substances. -Usually heating to a temperature between 150 and 220 C. is sufficient and the reaction proceeds in most cases quickly enough for technical purposes when heating to about 190 C. The quantity employed of the hydroxyl bearing orgamc compounds should correspond to about one half of that corresponding to the saponification value acid component, but a'higher quantity ma also be employed. According to the metho of production these plastic products possess the properties of linoxyn or rubber oil substitute and are well adapted for employment for example in the manufacture of linoleum or for filling or-improving rubber products, lacartificial masses and the like. The following may be mentioned among others as suitable organic compounds containin hydroxyl groups z-glycols, ethers of glycols with the same or other glycols, glycerol, mannitol, sorbitol, glucose and the like.

The treatment may be carried out in any known and suitable apparatus if desired in the presence of catalysts splitting off water, and/or with admixture with other substances 1929, Serial No. 388,185, and in Germany .ple metal compounds,

trate the nature of the invention but use is, 1928.

1930. Serial No. 469,250.

and at normal, increased or reduced ressures,

suitable substances to be added are or examas for example lead oxide and the like, which with the said acids give'agents of siccative action, or also a sulphurizing substance such as sulphur or compounds containin sulphur and the like. The said acids may a so be heated in admixture with unsaturated acids for example linoleic acid or with hydroxy carboxylic acids, such as ricinoleic acid, which are equivalents to the unsaturated-acids inasmuch as the are capable of forming unsaturated aci s by splitting off water or glycerides of the said acids. The process in accordance with the present invention may also be advantageously carried out by treating the acids or mixtures of acids with siccatives, i. e. compounds of the heavy metals, such as compounds of lead, manganese or cobalt or several of such compounds, or with sulphur previously to the esterification. In the treatment it is not necessary to employ the stoichiometrical quantity of hydroxyl compounds corresponding to an esterification of the organic acids present, but valuable plastic products are obtained by employing considerably smaller uantities, for example half of the theoretica y calculated quantity. It is advantageous to carry out the heat treatment at an elevated temperature in the liquid phase while passing through a gas or vapour such as nitrogen or carbon dioxide.-

The following examples will further illusvention is'not restricted to these examples. The parts are by weight.

' Eazample 1 I parts of the dark colored and liquid acid constituent of an oxidation product from parafiin hydrocarbons, obtainable by pressing the crude oxidation product, which is insoluble in petroleum ether and has a saponification value of 235, are heated together with 19.3 parts of glycerol at from to 210 centigrade in vacuo while stirring for an hour. After a further half an hour the mixture becomes viscous and finally solid. The

reaction product is a'dark, tenacious, nonthe in- 55 greasy, very elastic mass which is insoluble in alcohol, petroleumvether and acetone, soluble with difliculty in higher alcohols and ethers, and soluble in benzene, pyridine, trichlorethylene, and hot glacial acetic acid. It can be saponified with lyes.

Example 2 The substances described in Example 1 are mixed together in the same quantities with an addition of per cent of sulphur calculated with reference to the weight of acid employed. After heating this mixture at from 150. to 170 centigrade for 4 hours in vacuo while stirring, a deep black, crumbly mass which in other properties is similar to that described in Example 1 is obtained.

Example 3 150 parts of liquid acid product insoluble in petroleum ether and having a saponification value of 258, obtained from an oxidation product ofparaffin wax, are heated together with 2 per cent of lead oxide in vacuo at 160 centigrade while stirringfor 2 hours, and then after adding the calculated quantity of glycerol heated for a further 2 hours at from 200 to 210 centigrade. A product having similar properties to those described in'Example 1, but which has greater density and tenacity, is obtained.

Ezvample 4 The substances described in Example 1 are mixed in the quantities there given with an Example 5 150 parts of the liquid acid product having a saponification value of 258 described in Example 3 are heated together with 10.5 parts of glycerol for 2 hours in vacuo at from 170 to 200 centigrade while stirring. A product having similar properties to that described in Example 1, but having greater-tenacity, is obtained. Y

The present application has been divided out from our copending application Ser. N 0. 368,185, filed June 3, 1929.

What we claim is:

1. The process for the production of plastic masses which comprises heating the liquid acid portion, insoluble in petroleum ether, of a product of thedestructive oxidation of paraffin hydrocarbons, with a polyhydric alcohol to a temperature above about 150 centigrade in the presence of a sulphur-bearing vulcanizing agent.

2. The process for the production of plastic masses which comprises heating the liqui acid portion, insoluble in petroleum in petroleum ether,

ether, of a product of the destructive oxidation of paraflin hydrocarbons, with an unsaturated organic acid and a polyhydric alcohol to a temperature above about 150 centigrade in the presence of a sulphur-bearing vulcanizing agent.

3. Plastic tenacious masses comprising a heat reaction and sulphur-bearing vulcanization product of a mixture comprising esters of the acid constituents of the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of parafiin hydrocarbons, with a polyhydric alcohol.

4. Plastic tenacious masses comprising a heat reaction and sulphur-bearing vulcanization product of a mixture comprising esters of the acid constituents of the liquid acid portion,-insoluble in petroleum ether, of a product of the destructive oxidation of paraifin wax, with a polyhydric alcohol.

5. Plastic tenacious masses comprising a heat reaction and sulphur-bearing vulcanization product of a mixture comprising esters of the acid constituents of the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of paraffin w'ax, with glycerol.

6. The process for the production of plastic masses which comprises. heating at a temperature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of parafiin hydrocarbons, with an aliphatic compound containing at least two hydroxyl groups in its molecule, in the presence of a sulphur-bearing Vulcanizing agent.

7. The process for the production of plastic masses which comprises heating at a temperature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of paraflin wax, with an aliphatic compound containing at least two hydroxyl groups in. its molecule, in the presence of a sulphur-bearing vulcanizing agent.

8. The process for the production of plastic masses which comprises heatlng at a temperature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, having a saponification value rangingfrom about 235 to about 258, of a product of the destructive oxidation of paraiiin hydrocarbons, with an aliphatic compound containing at least two hydroxyl groups in its molecule, in the presence of a sulphur-bearing vulcanizing agent.

9. The process for the production of plastic masses which comprises heating at a temperature ranging from about 150 to about 240 C. the liquid acid portion, insoluble having a saponification value ranging from about 235 to about 258, of aproduct of the destructive oxidation of paraflin wax with an aliphatic compound the liquid acid portion,

containing at least two hydroxyl groups in its molecule, in the presence of a sulphurbearing vulcanizing agent.

10. The process for the production of plastic masses which comprises heating at a temperature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of paraflin hydrocarbons, with glycerol in the presence of a sulphur-bearing vulcanizing agent.

.11. The process for the production of plastic masses which comprises heating at a temerature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, having a saponification value ranging from about 235 to about 258, of a product of the destructive oxidation of paraflin wax with glycerol in the presence of a sulphur-bearing vulcanizing agent.

12. The process for the production of plastic masses which comprises heating at a temperature ranging from about 150 to 240 insoluble in petroleum ether, having a saponification value ranging from about 235 to about 258, of a product of the destructive oxidation of paraffin wax with glycerol in the presence of sulphur.

13. Plastic, tenacious masses comprising a heat reaction and sulphur-bearing.vulcanization product of the liquid soluble in petroleum ether,

acid portion, in-

of a product of the destructive oxidation of paraffin hydrocarbons, having a saponification value ranging from about 235 to about 258, with glycerol.

14. Plastic, tenacious masses comprising a heat reaction and sulphur-bearing vulcanization product of the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of paraffin wax, having a saponification value ranging from about 235 to about 258, with glycerol.

In testimony whereof we aflix our signatures MARTIN LUTHER. ROBERT HELD. 

